Electrons in metals

Modied 2010
PHYS208
May 21, 2010
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 1 / 22
The Drude Theory of metals
The Drude model is the application of ideal gas theory to electrons in a solid.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 2 / 22
Basic assumptions
Electrons move in static lattice of ions
Free electron approximation (neglect ion-electron interaction)
Independent electron approximation (neglect electron-electron interaction)
Some scattering mechanism exists, erasing all information of the electron
previous to the scattering event, giving each a random velocity determined by
the temperatur at the given position.
Probability of scattering during time interval t: t/, where is known as
the relaxation time.
Alternatively: the electrons move a distance before colliding (mean free
path).
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 3 / 22
Conductivity - static electric eld
If the electrons in a metal are subjected to a static
electric eld, they will tend to drift in the opposite
direction to the eld, with a drift velocity determined by
the eld. Since an electron has approximately a time to
be accelerated by the eld before a collision occurs, it will
gain a velocity v
drift
given by
v
drift
=
_

0
eE
m
dt =
eE
m
. (1)
This net displacement of electrons results in a nonzero current density j, which is
charge density velocity =
charge
unit volume
velocity (2)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 4 / 22
With N electrons of charge e in a volume V, and an average drift velocity v
drift
,
we arrive at
j =
eN
V

eE
m
=
Ne
2

mV
E. (3)
Ohms law gives us:
j = E. (4)
Where the proportionality constant is called the conductivity .
Written in terms of electrons per unit volume n = N/V, the conductivity becomes
=
ne
2

m
(5)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 5 / 22
Thermal conductivity
A temperature gradient in a slab of metal will induce a thermal current density. If
it is not too large, Fouriers law applies,

j = T. (6)
We want to calculate the thermal conductivity of metals.
We consider an oversimplied model, putting the z-direction along the
temperature gradient. An electron arriving at a point z will carry an energy given
by the temperature at its last collision site , (T[z cos ])
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 6 / 22
Thermal conductivity
The z-component of the velocity of carrier i is
(v
i
)
z
=
_

_
z
v = v cos
i
z, (7)
where v is the average velocity of the carriers.
1
v
1
l
1
l
1
u( r+ )
u( ) r
v
3
1
v
2
v
3
v
4
v
4
v
2
v
3
v
1
l
1
l
2
l
3
l
4
2
1
4
v
The current density due to carrier i is

j
i
=

J
in

J
out
=

J = (v
i
)
z
(u
r +l
i
u
r
) (8)
Where in represents the incomming current and out is the outgoing current,

j
i
= (v
i
)
z
u, (9)
where u is the dierence in energy density between to sites separated by

.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 7 / 22
Thermal conductivity

j
i
= v cos
i
_
u(r +

) u(r )
_
z (10)
= v cos
i
_
u

_
= v cos
i
_
u
z
cos
i
_
z
=
u
z
v cos
2

i
z.
To obtain the total current density we sum over i ,

j =

i
u
z
v cos
2

i
z. (11)
In stead of summing, we integrate over all solide angles d = sin dd,

j =
1
_
d
_
u
z
v cos
2
d z =
1
4
u
z
v
_
cos
2
d z, (12)
where
_
cos
2
d =
4
3
and
u
z
z =
u
T
T
z
z =
u
T
T = c
v
T
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 8 / 22
Thermal conductivity
Thus

j =
1
_
d
_
u
z
v cos
2
d =
_
1
3
c
v
v
_
T (13)
which, upon comparison with Fouriers law:

j = T. (14)
yields an expression for the thermal conductivity,
=
1
3
vc
v
=
1
3
v
2
c
v
(15)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 9 / 22
Wiedemann-Franz law
The Wiedemann-Franz law states that in a metal the ratio of thermal to electrical
conductivity is proportional to the temperature,

T, (16)
where =
1
3
v
2
c
v
and =
ne
2

m
as shown.
Ideal gas theory yields
1
2
mv
2
=
3
2
k
B
T, which gives the expression for spesic
heat capacity,
c
v
=
3
2
N
V
k
B
. (17)
Using the results from the Drude model, we can write the Lorenz number /T as

T
=
3
2
_
k
B
e
_
2
. (18)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 10 / 22
Wiedemann-Franz law
Calculated Lorenz number:

T
= 1.11 10
8
W
K
2
, (19)
which is about halv of the experimental values.
Experimental Lorenz numbers:
Figure: From Tony Harker, Chiranijib Mitra and Andrew Horseld, Solid State Physics
Notes
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 11 / 22
The ideal Fermi gas
To adequately describe electrons in metals, their quantum nature must be taken
into account.
Classical (Boltzmann) statisics insucient
Need to take into account Pauli exclusion principle
We consider a box of volume V = L
3
containing N electrons.
Under the assumption of no electron-electron interaction, the
wavefunction of the system factors into N components,
(r
1
, , r
N
) = (r
1
) (r
N
), each of which should satisfy
the time-independent Schrodinger equation,

2
2m
_

2
x
2
+

2
y
2
+

2
z
2
_
(r
i
) = (r
i
) (20)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 12 / 22
The ideal Fermi gas
The solutions are plane waves,

k
(r) e
ikr
, (21)
By choosing periodic (Born von-Karman) boundary conditions, ie,
(x + L) = (x) (22)
one gets discrete (one-electron) energy levels.
(k) =

2
k
2
2m
, k
i
=
2n
i
L
i
, n
i
= 0, 1, 2, ... (23)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 13 / 22
Fermi-Dirac distribution
The distribution of electrons in the
quantum gas is given by the Fermi-Dirac
distribution,
f() =
1
e
()/k
B
T
+ 1
(24)
Special case: T = 0. Then f() = 1 for

F
, zero elsewhere.
Very dierent from classical Boltzmann
distribution e
/k
B
T
for low
temperatures!
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 14 / 22
Density of states
For electrons (fermions), total number N is found by summing the mean
occupation number over all levels (factor 2 for spin),
N = 2

j
1
e
(
j
)/k
B
T
+ 1
(25)
If the box is very large, the energy spacing is very small. Thus we write,

j
1
e
(
j
)/k
B
T
+ 1
=
1
(k)
3

j
1
e
(
j
)/k
B
T
+ 1
(k)
3

L
3
(2)
3
_
(...)d
3
k
(26)
were we inserted k =
2
L
outside the sum and taken the limit k 0. Since f
only depends on the norm of k (through ), we introduce spherical coordinates,
and integrate out angular dependence, yielding a factor 4. We also replacing d
for dk.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 15 / 22
Density of states
Resulting expression for N:
N =
_
f()g()d (27)
N = 2
V
(2)
2
_
2m

2
_
3
2
_

1
2
f()d (28)
We identify the density of states g(),
g() = 2
V
(2)
2
_
2m

2
_
3
2

1
2
(29)
Number of one-electron states in an energy interval d is g()d.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 16 / 22
Fermi stu
Fermi wave vector, k
F
, the wave vector of the electron in the highest energy
state (T = 0).
Fermi momentum
p
F
= k
F
(30)
Fermi energy (typically 1.5 - 15 eV i metals)

F
=

2
k
2
F
2m
(31)
It can be shown that the fermi energy is proportional to the density of free
electrons in the metal.
Fermi temperature (of the order 10
5
for many metals)
T
F
=

F
k
B
(32)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 17 / 22
Sommerfeld integrals
Integrals of the type,
_

0
()f()d (33)
may be subject to the Sommereld expansion, if the temperatures are low enough
that f() is only non-constant in a very small interval around = . In that case,
we introduce:
() =
d()
d
. (34)
Integrating by parts, we nd
()f()|

0

_

0
df()
d
()d (35)
The rst part is zero since f ( ) = 0, and since our case ( 0) = 0.
Expanding () around = , and retaining only one term results in
_

0
d()
d
f()d = () +

2
3
(k
B
T)
2
2
d
2
()
d
2

=
(36)
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 18 / 22
Heat capacity of the electron gas
Both the phonons and the free electrons will contribute to the heat capacity of
metals.
c
total
v
= c
electr
v
+ c
phonons
v
(37)
We can calculate the specic heat capacity of an electron gas using Fermi-Dirac
statistics.
c
v
=
1
V
_
dU
dT
_
V
. (38)
The total energy is calculated by the integral
U =
_

0
dg()f(). (39)
We can evaluate the integral using Sommerfelds expansion.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 19 / 22
Heat capacity of the electron gas
We use the Sommerfeld expansion with one term,
_

0
d()
d
f()d = () +

2
3
(k
B
T)
2
2
d
2
()
d
2

=
(40)
U =
_

0
g() +

2
3
(k
B
T)
2
2
[g

() + g()] (41)
U = U
0
+

2
3
(k
B
T)
2
2
g(
F
), g(
F
) =
3
2
n

F
, T
F
=

F
K
B
(42)
and dierentiating the result, arriving at
c
electr
v
=

2
2
k
B
N
V
T
T
F
(43)
Notice linear temperature dependence.
Diers from classical result (ideal gas), c
classic
v
=
3
2
N
V
k
B
, by a factor

2
3
T
T
F
,
which is 0.01 at room temperature.
c
electr
v
has signicant contribution at low temperature, when c
phonons
v
T
3
.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 20 / 22
Why is the heat capacity of electrons in metals small?
Unless temperature is very high, only relatively few electrons near the Fermi
surface can change their state.
The remaining (majority) does not contribute to the heat capacity c
electr
v
.
In the classical gas, all electrons contribute, yielding a higher heat capacity.
The energy of the excited electrons is about
F
.
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 21 / 22
Lorenz number revisited
Lorenz number obtained from the new c
electr
v
:

T
=

2
3
_
k
B
e
_
2
= 2.45 10
8
W
K
2
. (44)
which is about the same as the experimental values.
Experimental Lorenz numbers:
Figure: From Tony Harker, Chiranijib Mitra and Andrew Horseld, Solid State Physics
Notes
PHYS208 () Electrons in metals Modied 2010 May 21, 2010 22 / 22